Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes
- Autores
- Deniz, Erhan; Tomasulo, Massimiliano; Cusido, Janet; Yildiz, Ibrahim; Petriella, Marco; Bossi, Mariano Luis; Sortino, Salvatore; Raymo, Françisco M.
- Año de publicación
- 2012
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- We synthesized five fluorophore-photochrome dyads designed to switch reversibly between nonfluorescent and fluorescent isomers under optical control. These compounds pair an oxazine photochrome to a biphenyl, fluorene, pyrene, coumarin, or cyanine fluorophore in their molecular skeleton and can be prepared in a single step from known precursors in yields ranging from 30 to 63%. Nuclear magnetic resonance spectroscopy indicates that the oxazine ring of these compounds opens and closes spontaneously on a millisecond time scale in acetonitrile at ambient temperature. Under these conditions, the fraction of ring-open isomer at equilibrium is negligible in all instances with the exception of the cyanine derivative, which instead is almost exclusively in this form. Absorption and emission spectroscopies demonstrate, however, that the fraction of ring-open isomer is sensitive to solvent polarity and increases with a transition from acetonitrile to methanol. Alternatively, the ring-open isomer can be populated photochemically or trapped with the addition of acid. In both instances, the characteristic absorption and emission bands of the 3H-indolium chromophores, embedded within the ring-open species, can clearly be observed in the visible region. In the case of the coumarin derivative, the brightness of this chromophoric fragment is sufficiently high to permit the imaging of individual molecules with excellent signal-to-noise ratios. In fact, the fluorescence of single fluorophore-photochrome dyads can be activated under the influence of ultraviolet inputs and the resulting species can be localized with nanoscale precision under visible illumination. Indeed, subdiffraction images of polymer nanoparticles, doped with this particular dyad, can be reconstructed with nanoscale resolution. Thus, our operating principles for fluorescence switching at the single-molecule level can offer the opportunity to overcome diffraction and, eventually, lead to the development of an entire family of probes for super-resolution fluorescence imaging. © 2012 American Chemical Society.
Fil: Deniz, Erhan. University of Miami; Estados Unidos
Fil: Tomasulo, Massimiliano. University of Miami; Estados Unidos
Fil: Cusido, Janet. University of Miami; Estados Unidos
Fil: Yildiz, Ibrahim. University of Miami; Estados Unidos
Fil: Petriella, Marco. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Bossi, Mariano Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Sortino, Salvatore. University of Catania; Italia
Fil: Raymo, Françisco M.. University of Miami; Estados Unidos - Materia
-
Fluorescence
Photochemistry
Photoswitching
Nanoscopy - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
- Repositorio
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/67811
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Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine AuxochromesDeniz, ErhanTomasulo, MassimilianoCusido, JanetYildiz, IbrahimPetriella, MarcoBossi, Mariano LuisSortino, SalvatoreRaymo, Françisco M.FluorescencePhotochemistryPhotoswitchingNanoscopyhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We synthesized five fluorophore-photochrome dyads designed to switch reversibly between nonfluorescent and fluorescent isomers under optical control. These compounds pair an oxazine photochrome to a biphenyl, fluorene, pyrene, coumarin, or cyanine fluorophore in their molecular skeleton and can be prepared in a single step from known precursors in yields ranging from 30 to 63%. Nuclear magnetic resonance spectroscopy indicates that the oxazine ring of these compounds opens and closes spontaneously on a millisecond time scale in acetonitrile at ambient temperature. Under these conditions, the fraction of ring-open isomer at equilibrium is negligible in all instances with the exception of the cyanine derivative, which instead is almost exclusively in this form. Absorption and emission spectroscopies demonstrate, however, that the fraction of ring-open isomer is sensitive to solvent polarity and increases with a transition from acetonitrile to methanol. Alternatively, the ring-open isomer can be populated photochemically or trapped with the addition of acid. In both instances, the characteristic absorption and emission bands of the 3H-indolium chromophores, embedded within the ring-open species, can clearly be observed in the visible region. In the case of the coumarin derivative, the brightness of this chromophoric fragment is sufficiently high to permit the imaging of individual molecules with excellent signal-to-noise ratios. In fact, the fluorescence of single fluorophore-photochrome dyads can be activated under the influence of ultraviolet inputs and the resulting species can be localized with nanoscale precision under visible illumination. Indeed, subdiffraction images of polymer nanoparticles, doped with this particular dyad, can be reconstructed with nanoscale resolution. Thus, our operating principles for fluorescence switching at the single-molecule level can offer the opportunity to overcome diffraction and, eventually, lead to the development of an entire family of probes for super-resolution fluorescence imaging. © 2012 American Chemical Society.Fil: Deniz, Erhan. University of Miami; Estados UnidosFil: Tomasulo, Massimiliano. University of Miami; Estados UnidosFil: Cusido, Janet. University of Miami; Estados UnidosFil: Yildiz, Ibrahim. University of Miami; Estados UnidosFil: Petriella, Marco. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Bossi, Mariano Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Sortino, Salvatore. University of Catania; ItaliaFil: Raymo, Françisco M.. University of Miami; Estados UnidosAmerican Chemical Society2012-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/67811Deniz, Erhan; Tomasulo, Massimiliano; Cusido, Janet; Yildiz, Ibrahim; Petriella, Marco; et al.; Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes; American Chemical Society; Journal of Physical Chemistry C; 116; 10; 3-2012; 6058-60681932-7447CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp211796pinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp211796pinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:46:18Zoai:ri.conicet.gov.ar:11336/67811instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-03 09:46:18.554CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes |
title |
Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes |
spellingShingle |
Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes Deniz, Erhan Fluorescence Photochemistry Photoswitching Nanoscopy |
title_short |
Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes |
title_full |
Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes |
title_fullStr |
Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes |
title_full_unstemmed |
Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes |
title_sort |
Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes |
dc.creator.none.fl_str_mv |
Deniz, Erhan Tomasulo, Massimiliano Cusido, Janet Yildiz, Ibrahim Petriella, Marco Bossi, Mariano Luis Sortino, Salvatore Raymo, Françisco M. |
author |
Deniz, Erhan |
author_facet |
Deniz, Erhan Tomasulo, Massimiliano Cusido, Janet Yildiz, Ibrahim Petriella, Marco Bossi, Mariano Luis Sortino, Salvatore Raymo, Françisco M. |
author_role |
author |
author2 |
Tomasulo, Massimiliano Cusido, Janet Yildiz, Ibrahim Petriella, Marco Bossi, Mariano Luis Sortino, Salvatore Raymo, Françisco M. |
author2_role |
author author author author author author author |
dc.subject.none.fl_str_mv |
Fluorescence Photochemistry Photoswitching Nanoscopy |
topic |
Fluorescence Photochemistry Photoswitching Nanoscopy |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
dc.description.none.fl_txt_mv |
We synthesized five fluorophore-photochrome dyads designed to switch reversibly between nonfluorescent and fluorescent isomers under optical control. These compounds pair an oxazine photochrome to a biphenyl, fluorene, pyrene, coumarin, or cyanine fluorophore in their molecular skeleton and can be prepared in a single step from known precursors in yields ranging from 30 to 63%. Nuclear magnetic resonance spectroscopy indicates that the oxazine ring of these compounds opens and closes spontaneously on a millisecond time scale in acetonitrile at ambient temperature. Under these conditions, the fraction of ring-open isomer at equilibrium is negligible in all instances with the exception of the cyanine derivative, which instead is almost exclusively in this form. Absorption and emission spectroscopies demonstrate, however, that the fraction of ring-open isomer is sensitive to solvent polarity and increases with a transition from acetonitrile to methanol. Alternatively, the ring-open isomer can be populated photochemically or trapped with the addition of acid. In both instances, the characteristic absorption and emission bands of the 3H-indolium chromophores, embedded within the ring-open species, can clearly be observed in the visible region. In the case of the coumarin derivative, the brightness of this chromophoric fragment is sufficiently high to permit the imaging of individual molecules with excellent signal-to-noise ratios. In fact, the fluorescence of single fluorophore-photochrome dyads can be activated under the influence of ultraviolet inputs and the resulting species can be localized with nanoscale precision under visible illumination. Indeed, subdiffraction images of polymer nanoparticles, doped with this particular dyad, can be reconstructed with nanoscale resolution. Thus, our operating principles for fluorescence switching at the single-molecule level can offer the opportunity to overcome diffraction and, eventually, lead to the development of an entire family of probes for super-resolution fluorescence imaging. © 2012 American Chemical Society. Fil: Deniz, Erhan. University of Miami; Estados Unidos Fil: Tomasulo, Massimiliano. University of Miami; Estados Unidos Fil: Cusido, Janet. University of Miami; Estados Unidos Fil: Yildiz, Ibrahim. University of Miami; Estados Unidos Fil: Petriella, Marco. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina Fil: Bossi, Mariano Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina Fil: Sortino, Salvatore. University of Catania; Italia Fil: Raymo, Françisco M.. University of Miami; Estados Unidos |
description |
We synthesized five fluorophore-photochrome dyads designed to switch reversibly between nonfluorescent and fluorescent isomers under optical control. These compounds pair an oxazine photochrome to a biphenyl, fluorene, pyrene, coumarin, or cyanine fluorophore in their molecular skeleton and can be prepared in a single step from known precursors in yields ranging from 30 to 63%. Nuclear magnetic resonance spectroscopy indicates that the oxazine ring of these compounds opens and closes spontaneously on a millisecond time scale in acetonitrile at ambient temperature. Under these conditions, the fraction of ring-open isomer at equilibrium is negligible in all instances with the exception of the cyanine derivative, which instead is almost exclusively in this form. Absorption and emission spectroscopies demonstrate, however, that the fraction of ring-open isomer is sensitive to solvent polarity and increases with a transition from acetonitrile to methanol. Alternatively, the ring-open isomer can be populated photochemically or trapped with the addition of acid. In both instances, the characteristic absorption and emission bands of the 3H-indolium chromophores, embedded within the ring-open species, can clearly be observed in the visible region. In the case of the coumarin derivative, the brightness of this chromophoric fragment is sufficiently high to permit the imaging of individual molecules with excellent signal-to-noise ratios. In fact, the fluorescence of single fluorophore-photochrome dyads can be activated under the influence of ultraviolet inputs and the resulting species can be localized with nanoscale precision under visible illumination. Indeed, subdiffraction images of polymer nanoparticles, doped with this particular dyad, can be reconstructed with nanoscale resolution. Thus, our operating principles for fluorescence switching at the single-molecule level can offer the opportunity to overcome diffraction and, eventually, lead to the development of an entire family of probes for super-resolution fluorescence imaging. © 2012 American Chemical Society. |
publishDate |
2012 |
dc.date.none.fl_str_mv |
2012-03 |
dc.type.none.fl_str_mv |
info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo |
format |
article |
status_str |
publishedVersion |
dc.identifier.none.fl_str_mv |
http://hdl.handle.net/11336/67811 Deniz, Erhan; Tomasulo, Massimiliano; Cusido, Janet; Yildiz, Ibrahim; Petriella, Marco; et al.; Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes; American Chemical Society; Journal of Physical Chemistry C; 116; 10; 3-2012; 6058-6068 1932-7447 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/67811 |
identifier_str_mv |
Deniz, Erhan; Tomasulo, Massimiliano; Cusido, Janet; Yildiz, Ibrahim; Petriella, Marco; et al.; Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes; American Chemical Society; Journal of Physical Chemistry C; 116; 10; 3-2012; 6058-6068 1932-7447 CONICET Digital CONICET |
dc.language.none.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp211796p info:eu-repo/semantics/altIdentifier/doi/10.1021/jp211796p |
dc.rights.none.fl_str_mv |
info:eu-repo/semantics/openAccess https://creativecommons.org/licenses/by-nc-sa/2.5/ar/ |
eu_rights_str_mv |
openAccess |
rights_invalid_str_mv |
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/ |
dc.format.none.fl_str_mv |
application/pdf application/pdf application/pdf |
dc.publisher.none.fl_str_mv |
American Chemical Society |
publisher.none.fl_str_mv |
American Chemical Society |
dc.source.none.fl_str_mv |
reponame:CONICET Digital (CONICET) instname:Consejo Nacional de Investigaciones Científicas y Técnicas |
reponame_str |
CONICET Digital (CONICET) |
collection |
CONICET Digital (CONICET) |
instname_str |
Consejo Nacional de Investigaciones Científicas y Técnicas |
repository.name.fl_str_mv |
CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas |
repository.mail.fl_str_mv |
dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar |
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1842268785783865344 |
score |
13.13397 |